Bio-Based Terephthalate Polyesters

ABSTRACT

Bio-based terephthalic acid (bio-TPA), bio-based dimethyl terephthalate (bio-DMT), and bio-based polyesters, which are produced from a biomass containing a terpene or terpenoid, such as limonene are described, as well as the process of making these products. The bio-based polyesters include poly(alkylene terephthalate)s such as bio-based poly(ethylene terephthalate) (bio-PET), bio-based poly(trimethylene terephthalate) (bio-PTT), bio-based poly(butylene terephthalate) (bio-PBT), and bio-based poly(cyclohexylene dimethyl terephthalate) (bio-PCT).

Several scientific studies strongly suggest that petroleum feed stockswill be exhausted around year 2050 if the present consumption of fossilstocks will continue at a constant rate. See, for example, US Departmentof Energy: Top value Added Chemicals from biomass. Vol 1. August 2004;Okkerse, C. et al., Green Chemistry (1999), 1(2), 107-114; and Corma,A., et al., Chemical Reviews (2007), 107(6), 2411-2502.

The Kyoto protocol together with the desire to reduce society'sdependence on imported crude oil has directed researcher's attentiontoward the use of biomass as source of energy and of commoditychemicals. Further, the cost of petroleum feed stocks has risendramatically and there is a rising consumer interest in using “green”,or renewable resources as the basis for consumer products.

Therefore, the era of a chemical industry based on fossil resources willprobably come to an end before the end of the century.

Terephthalic acid, is a commodity chemical, principally used as astarting compound for the manufacture of various polyesters,specifically poly(ethylene terephthalate) (PET), which is used inclothing and to make plastic bottles. Terephthalic acid is produced onan industrial scale by oxidation of para-xylene by oxygen from air inthe presence of a catalyst. However, this synthetic route toterephthalic acid and poly(terephthalates) will either becomeprohibitively expensive, as the cost of petroleum rises, or unavailableas petroleum resources become scarce.

Nature produces a vast amount of biomass per year by photosynthesis.See, e.g., Corma, A., et al., Chemical Reviews (2007), 107(6),2411-2502. Terpenes are a large and varied class of naturally occurringhydrocarbons that are formed by units of isoprene ordered in a regularpattern. Terpenes and other terpenoids are produced primarily by a widevariety of plants and are a natural and sustainable supply of chemicalbuilding blocks. For example, world production of turpentine oil in 1995was 330000 tons while limonene production was around 30000 tons peryear. See, e.g., Swift K. A. D., Topics in Catalysis (2004), 27(1-4),143-155.

As described above, terpenes are available as potential candidates fornatural feedstock, or bio-based chemicals. However, the use of terpenesas a natural feedstock to prepare aromatic groups, such as terephthalicacid (TPA), to be used for the preparation of thermoplastic polyestersis not currently known.

Therefore, there is a need for bio-based polyesters, produced from abiomass source. There is also a need for bio-based terephthalic acid andbio-based dimethyl terephthalate, produced from a biomass source, toproduce the bio-based polyesters, such as PET and otherpoly(terephthalates).

SUMMARY

Bio-based terephthalic acid, bio-based dimethyl terephthalate, andbio-based polyesters are described herein. The compounds and processesdescribed herein satisfy the above-described need for bio-basedpolyesters, bio-based terephthalic acid, and bio-based dimethylterephthalate, which are produced from a biomass source.

According to one embodiment, a bio-based terephthalic acid of Formula Iis provided.

Wherein the bio-based terephthalic acid has a mean bio-based content ofat least 5%. Preferably, the bio-based terephthalic acid has a meanbio-based content of at least 80%, and more preferably, of at least 90%.

According to one embodiment, the bio-based terephthalic acid of FormulaI is prepared from a biomass. According to the process, first a“biomass”, which is a biological material excluding organic materialthat has been transformed by geological processes into a member selectedfrom the group consisting of petroleum, petrochemicals, and combinationsthereof is provided. The biomass is then converted to terephthalic acid,preferably substantially in the absence of chromium oxide.

Preferably, the process of making the bio-based terephthalic acid ofFormula I comprises providing a biomass comprising a terpene, terpenoidor a mixture thereof, and converting the terpene, terpenoid, or mixturethereof to para-cymene. The para-cymene is then converted toterephthalic acid by oxidation, the oxidation being performedsubstantially in the absence of chromium oxide.

The oxidation step is preferably a two-step oxidation, and morepreferably, a two step oxidation comprising a first step using a mineralacid, and a second step using a transition metal oxidant, such as apermanganate compound. Also preferably, the process is performedsubstantially in the absence of chromium, and the oxidation step has atotal yield of at least 85%.

Preferably, the terpene or terpenoid has a mono-cyclic or bi-cyclicstructure, and/or the terpene or terpenoid has ten carbon atoms in thechemical formula. The terpene or terpenoid may be selected from thegroup consisting of borneol, camphene, camphor, careen, camphene,carvacrol, carvone, cineole, eucalyptol, limonene, phellandrene,dipentene, pinene, sabinene, terpineol, terpinene, terpinolene, thujene,thymol, and combinations thereof. More preferably, the terpene islimonene.

The terpene, terpenoid, or mixture thereof may be converted topara-cymene in the presence of a catalyst selected from the groupconsisting of metal catalysts, amine catalysts, and combinationsthereof. Also, the terpene, terpenoid, or mixture thereof may beconverted to para-cymene in the presence of a catalyst selected from thegroup consisting of transition metal catalysts, Group IA catalysts,amine catalysts, and combinations thereof. Preferably, the para-cymeneis produced at a yield of at least 70% from the terpene, terpenoid, orcombination thereof, more preferably, at a yield of at least 95% fromthe terpene, terpenoid, or combination thereof.

According to another embodiment of the invention, a compound comprisingbio-based dimethyl terephthalate of Formula II is provided.

The bio-based dimethyl terephthalate has a mean bio-based content of atleast 5%. Preferably, the bio-based dimethyl terephthalate has a meanbio-based content at least 80%, and more preferably, at least 90%.

The bio-based dimethyl terephthalate may be made by a process comprisingconverting bio-based terephthalic acid to bio-based dimethylterephthalate by esterification of the bio-based terephthalic acid.Alternately, the bio-based dimethyl terephthalate of Formula II may beprepared by a process comprising first providing a biomass as describedabove, and then converting the biomass to bio-based terephthalic acid ofFormula I.

Preferably, the process of making bio-based dimethyl terephthalate ofFormula II comprises first providing a biomass comprising a terpene,terpenoid or a mixture thereof, and then converting the terpene,terpenoid, or mixture thereof to bio-based para-cymene. The bio-basedpara-cymene is then converted to bio-based terephthalic acid of FormulaI by an oxidation performed substantially in the absence of chromiumoxide, and then the bio-based terephthalic acid with methanol selectedfrom the group consisting of bio-based methanol, petroleum basedmethanol, and combinations thereof to provide the bio-based dimethylterephthalate of Formula II. More preferably, the bio-based terephthalicacid of Formula I is converted to bio-based dimethyl terephthalate ofFormula II with bio-based methanol, the bio-based methanol having a meanbio-based content of at least 90%.

According to another embodiment, the process further comprises mixingthe bio-based terephthalic acid of Formula I with petroleum basedterephthalic acid to make a mixture of bio-based terephthalic acid andpetroleum based terephthalic acid.

According to another embodiment of the invention, a polymer compoundcomprising bio-based poly(alkylene terephthalate) of Formula III isprovided.

Wherein R₁ is selected from the group consisting of alkyl, cycloalkyl,cycloalkylene alkyl, and cycloalkylene dialkyl groups having from two toten carbons, and n is an integer between about 50 and about 130.

The bio-based poly(alkylene terephthalate) of Formula III has a meanbio-based content of at least 5%. Preferably, the bio-basedpoly(alkylene terephthalate) of Formula III has a mean bio-based contentof at least 60%, more preferably, at least 80%, and most preferably, atleast 90%.

According to one embodiment of the invention, in the compound of FormulaIII, R₁ is a bio-based group selected from the group consisting ofbio-based alkyl, bio-based cycloalkyl, bio-based cycloalkylene alkyl,and bio-based cycloalkylene dialkyl groups having from two to tencarbons. According to another embodiment, R₁ is an alkyl group of theformula —(CH₂)_(m)—, wherein m is an integer from two to four, andpreferably, R₁ is a bio-based alkyl group of the formula —(CH₂)_(m)—,wherein m is an integer from two to four. According to anotherembodiment R₁ may also be a cycloalkylene dialkyl group, preferably,according to this embodiment, R₁ is a bio-based cycloalkylene dialkylgroup.

According to another embodiment of the invention, a process forpreparing a bio-based poly(alkylene terephthalate) of Formula III isprovided. According to the process, first, a biomass, as describedabove, is provided. The biomass is then converted to bio-basedterephthalic acid, and the bio-based terephthalic acid is then convertedto the bio-based poly(alkylene terephthalate) of Formula III.

According to another embodiment, the process of converting the bio-basedterepththalic acid is performed by first converting the bio-basedterephthalic acid to bio-based dimethyl terephthalate.

According to another embodiment, the bio-based dimethyl terepththalateand/or terephthalic acid is converted to the bio-based poly(alkyleneterephthalate) of Formula III by reacting the bio-based dimethylterephthalate and/or terephthalic acid with a diol of the formula:

HO—R₁—OH

Where R₁ is an alkyl group of the formula —(CH₂)_(m)—, wherein m is aninteger from two to four. Preferably, the diol is at least in part abio-based diol, the diol having a mean bio-based content of at least80%.

According to another embodiment of the invention, a polymer compoundcomprising bio-based poly(butylene terephthalate) of Formula IV isprovided.

Wherein n is an integer of between about 50 and about 130.

The bio-based poly(butylene terephthalate) of Formula IV has a meanbio-based content of at least 5%. Preferably, the bio-basedpoly(butylene terephthalate) has a mean bio-based content of at least50%, more preferably, at least 80%, and most preferably, at least 90%,the bio-based poly(butylene terephthalate) is made by a processcomprising reacting bio-based dimethyl terephthalate with 1,4-butanediol.

According to another embodiment of the invention, the bio-basedpoly(butylene terephthalate) of Formula IV may be prepared by reactingthe bio-based dimethyl terephthalate of Formula II and/or terephthalicacid of Formula I with 1,4-butane diol. In a preferred embodiment, thebio-based poly(butylene terephthalate) of Formula IV is made by aprocess comprising reacting bio-based dimethyl terephthalate with1,4-butane diol selected from the group consisting of petroleum based1,4-butane diol, bio-based 1,4-butane diol, and combinations thereof.More preferably, the bio-based poly(butylene terephthalate) is made by aprocess comprising reacting bio-based dimethyl terephthalate with a1,4-butane diol that is at least in part bio-based 1,4-butane diol.

According to another embodiment of the invention, a polymer compoundcomprising bio-based poly(trimethylene terephthalate) of Formula V isprovided.

Wherein n is an integer of between about 50 and 130.

The bio-based poly(trimethylene terephthalate) of Formula IV has a meanbio-based content of at least 5%. Preferably, the bio-basedpoly(trimethylene terephthalate) has a mean bio-based content of atleast 33%, more preferably, of at least 80%, and most preferably, of atleast 90%.

According to another embodiment of the invention, the bio-basedpoly(trimethylene terephthalate) of Formula IV may be prepared byreacting the bio-based dimethyl terephthalate of Formula II and/orterephthalic acid of Formula I with 1,3-propane diol. In a preferredembodiment, the bio-based poly(trimethylene terephthalate) is made by aprocess comprising reacting bio-based dimethyl terephthalate with1,3-propane diol selected from the group consisting of petroleum based1,3-propane diol, bio-based 1,3-propane diol, and combinations thereof.More preferably, the 1,3-propane diol is at least in part bio-based1,3-propane diol, and most preferably, the 1,3-propane diol is at leastin part bio-based 1,3-propane diol, the 1,3-propane diol having a meanbio-based content of at least 80%.

According to another embodiment of the invention, a polymer compoundcomprising bio-based poly(ethylene terephthalate) of Formula VI isprovided.

Wherein n is an integer of between about 50 and about 130; and

The bio-based poly(ethylene terephthalate) of Formula VI has a meanbio-based content of at least 5%. Preferably, the bio-basedpoly(ethylene terephthalate) has a mean bio-based content of at least33%, more preferably, at least 80%, and most preferably, at least 90%.

According to another embodiment of the invention, the bio-basedpoly(ethylene terephthalate) of Formula VI may be prepared by reactingthe bio-based dimethyl terephthalate of Formula II and/or terephthalicacid of Formula I with ethylene glycol. In a preferred embodiment, thebio-based poly(ethylene terephthalate) is made by a process comprisingreacting bio-based dimethyl terephthalate with ethylene glycol selectedfrom the group consisting of petroleum based ethylene glycol, bio-basedethylene glycol, and combinations thereof. Preferably, the bio-basedpoly(ethylene terephthalate) is made by a process comprising reactingbio-based dimethyl terephthalate with ethylene glycol that is at leastin part bio-based ethylene glycol, and more preferably, the ethyleneglycol is at least in part bio-based ethylene glycol, having a meanbio-based content of at least 80%.

According to another embodiment of the invention, a compound comprisingbio-based 1,4-cyclohexane dimethanol of Formula VII is provided.

The bio-based 1,4-cyclohexane dimethanol has a mean bio-based content ofat least 5%. Preferably, the bio-based 1,4-cyclohexane dimethanol has amean bio-based content of at least 80%, and more preferably, at least90%.

According to another embodiment of the invention, a process of making acompound comprising bio-based 1,4-cyclohexane dimethanol of Formula VIIis provided. According to the process, first, a biomass, as describedabove, comprising a terpene, terpenoid or a mixture thereof is provided.Then, the terpene, terpenoid, or mixture thereof is converted topara-cymene, and the para-cymene is converted to terephthalic acid byoxidation, the oxidation being performed in the absence of chromiumoxide. The terephthalic acid is then converted to the bio-based1,4-cyclohexane dimethanol of Formula VII.

According to another embodiment of the invention, a polymer compoundcomprising bio-based poly(cyclohexylene dimethylene terephthalate) ofFormula VIII is provided.

Wherein n is an integer between about 50 and about 130.

The bio-based poly(cyclohexylene dimethylene terephthalate) has a meanbio-based content of at least 5%. Preferably, the bio-basedpoly(cyclohexylene dimethylene terephthalate) has a mean bio-basedcontent of at least 80%, and more preferably, at least 90%.

According to another embodiment of the invention, the bio-basedpoly(cyclohexylene dimethylene terephthalate) of Formula VIII may beprepared by reacting the bio-based dimethyl terephthalate of Formula IIand/or terephthalic acid of Formula I with 1,4-cyclohexane. In apreferred embodiment, the bio-based poly(cyclohexylene dimethyleneterephthalate) is made by a process comprising reacting bio-baseddimethyl terephthalate with a 1,4-cyclohexane dimethanol selected fromthe group consisting of petroleum based 1,4-cyclohexane dimethanol,bio-based 1,4-cyclohexane dimethanol, and combinations thereof. Alsopreferably, the bio-based dimethyl terephthalate has a mean bio-basedcontent of at least 5%, and/or the bio-based 1,4-cyclohexane dimethanolhas a mean bio-based content of at least 5%. More preferably, thebio-based dimethyl terephthalate has a mean bio-based content of atleast 80%, and/or the bio-based 1,4-cyclohexane dimethanol has a meanbio-based content of at least 80%, and most preferably, the bio-baseddimethyl terephthalate has a mean bio-based content of at least 90%,and/or the bio-based 1,4-cyclohexane dimethanol has a mean bio-basedcontent of at least 90%.

DESCRIPTION

According to one embodiment of the present invention, a biomass, such asterpenes and terpenoids, and mixtures thereof, is converted to bio-basedterephthalic acid (TPA) and bio-based di-methyl terephthalate (DMT). Inparticular, both α- and β-pinene, the main component of turpentine oil,and limonene, the main component of lemon essential oil, posses a sixmember hydrocarbon ring. As described herein, these terpenes are anavailable biomass source, and may be transformed into six member ringaromatic compounds such as para-cymene, which is then converted tobio-based terephthalic acid (bio-TPA) and bio-based di-methylterephthalate (bio-DMT). The bio-TPA and bio-DMT may be subsequentlypolymerized to form bio-based polyesters, such as bio-basedpoly(ethylene terephthalate) (bio-PET), bio-based poly(trimethyleneterephthalate) (bio-PTT), and bio-based poly(butylene terephthalate)(bio-PBT). A biomass is also converted to bio-based cyclohexanedi-methanol and polymerized with bio-based terephthalic acid orbio-based di-methyl terephthalate (bio-DMT) to produce bio-basedpoly(cyclohexylene dimethyl terephthalate) (bio-PCT).

As used in this disclosure, the following terms have the followingmeanings:

The term “bio-based” means a compound, composition and/or other organicmaterial that is “isotopically rich” in carbon 14 as compared to apetroleum source, as determined by ASTM D6866.

The term “bio-mass” means living and recently dead biological materialwhich excludes organic material that has been transformed by geologicalprocesses into a member selected from the group consisting of petroleum,petrochemicals, and combinations thereof.

The term “isotopically rich” means a higher carbon 14 to carbon 12 ratioin a compound, composition and/or other organic material as compared tothe carbon 14 to carbon 12 ratio in a petroleum source.

Other than in the operating examples or where otherwise indicated, allnumbers or expressions referring to quantities of ingredients, reactionconditions, and the like, used in the specification and claims are to beunderstood as modified in all instances by the term “about.” Variousnumerical ranges are disclosed in this patent application. Because theseranges are continuous, they include every value between the minimum andmaximum values. The endpoints of all ranges reciting the samecharacteristic or component are independently combinable and inclusiveof the recited endpoint. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations. The term “from more than 0 to” an amount means that thenamed component is present in some amount more than 0, and up to andincluding the higher named amount.

According to one embodiment of the present invention, there is providedbio-based terephthalic acid of Formula I:

According to this embodiment of the invention, at least 5% of theterephthalic acid of formula I is bio-based terephthalic acid. In apreferred embodiment, at least 80% of the terephthalic acid of formula Iis bio-based terephthalic acid, and more preferably, at least 90% of theterephthalic acid of formula I is bio-based terephthalic acid.

The bio-based terephthalic acid of formula I is prepared from a biomasswhich is converted, substantially in the absence of chromium oxide tothe bio-based terephthalic acid of Formula I.

According to another embodiment of the invention, a bio-based dimethylterephthalate of Formula II is provided:

According to this embodiment of the invention at least 5% of thedimethyl terephthalate is bio-based dimethyl terephthalate, and morepreferably, at least 80% of the dimethyl terephthalate is bio-baseddimethyl terephthalate, and most preferably, at least 90% of thedimethyl terephthalate is bio-based dimethyl terephthalate.

The bio-based dimethyl terephthalate of Formula II is prepared byconverting the bio-based terephthalic acid to bio-based dimethylterephthalate of Formula II with methanol. The methanol may be bio-basedmethanol, petroleum based methanol, and/or a combinations thereof.

The bio-based terephthalic acid (bio-TPA) of Formula I and the bio-baseddimethyl terephthalate (bio-DMT) of Formula II may be converted tovarious bio-based polyesters, such as poly(ethylene terephthalate)(bio-PET), poly(trimethylene terephthalate) (bio-PTT), and poly(butyleneterephthalate) (bio-PBT). A biomass, as described herein, may also beconverted to bio-based cyclohexane di-methanol and converted withbio-based terephthalic acid (bio-TPA) or bio-based di-methylterephthalate (bio-DMT) to produce bio-based poly(cyclohexylene dimethylterephthalate) (bio-PCT). However, other polymers may be produced withthe compounds and methods described herein, as will be understood bythose of skill in the art by reference to this disclosure.

According to another embodiment of the invention a polymer compoundcomprising bio-based poly(alkylene terephthalate) of Formula III isprovided.

wherein

-   -   R₁ is selected from the group consisting of alkyl, cycloalkyl,        cycloalkylene alkyl, and cycloalkylene dialkyl groups having        from two to ten carbons,    -   n is an integer between about 50 and about 130; and

In the bio-based poly(alkylene terephthalate) represented by Formula IIIabove, at least 5% of the poly(alkylene terephthalate) is bio-basedpoly(alkylene terephthalate). Preferably, at least 60% of thepoly(alkylene terephthalate) is bio-based poly(alkylene terephthalate),and more preferably, at least 80% of the poly(alkylene terephthalate) isbio-based poly(alkylene terephthalate), and most preferably, at least90% of the poly(alkylene terephthalate) is bio-based poly(alkyleneterephthalate).

In the bio-based poly(alkylene terephthalate) represented by FormulaIII, R₁ is petroleum based, bio-based, or a combination thereof. In apreferred embodiment, R₁ is a bio-based group selected from the groupconsisting of bio-based alkyl, bio-based cycloalkyl, bio-basedcycloalkylene alkyl, and bio-based cycloalkylene dialkyl groups havingfrom two to ten carbons, and R₁ is a bio-based or petroleum based alkylgroup of the formula —(CH₂)_(m)—, wherein m is an integer from two tofour, or R₁ is a bio-based or petroleum based cycloalkylene dialkylgroup. More preferably, R₁ is a bio-based alkyl group of the formula—(CH₂)_(m)—, wherein m is an integer from two to four, such as bio-basedethyl, propyl, and butyl substituents, or R₁ is a bio-basedcycloalkylene dialkyl group, such as bio-based cyclohexylene dimethyl.

According to another embodiment of the invention a polymer compoundcomprising bio-based poly(butylene terephthalate) of Formula IV isprovided.

wherein n is an integer of between about 50 and about 130.

In the bio-based poly(butylene terephthalate) of Formula IV above, atleast 5% of the poly(butylene terephthalate) is bio-based poly(butyleneterephthalate). Preferably, at least 50% of the poly(butyleneterephthalate) is bio-based poly(butylene terephthalate). Morepreferably, at least 80% of the poly(butylene terephthalate) isbio-based poly(butylene terephthalate), and most preferably, at least90% of the poly(butylene terephthalate) is bio-based poly(butyleneterephthalate).

The butylene group, —(CH₂)₂—, as shown in the Formula IV above may bepetroleum based, bio-based, or a combinations thereof, with bio-basedbutylene, —(CH₂)₂—, being preferred.

According to another embodiment of the invention, a polymer compoundcomprising bio-based poly(trimethylene terephthalate) of Formula V isprovided.

wherein n is an integer of between about 50 and 130.

In the bio-based poly(trimethylene terephthalate) of Formula V, at least5% of the poly(trimethylene terephthalate) is bio-basedpoly(trimethylene terephthalate). Preferably, at least 33% of thepoly(trimethylene terephthalate) is bio-based poly(trimethyleneterephthalate). More preferably, at least 80% of the poly(trimethyleneterephthalate) is bio-based poly(trimethylene terephthalate), and mostpreferably, at least 90% of the poly(trimethylene terephthalate) isbio-based poly(trimethylene terephthalate).

The trimethylene group, —(CH₂)₃—, as shown in the Formula V above may bepetroleum based, bio-based, or a combinations thereof, with bio-basedtrimethylene, —(CH₂)₃—, being preferred.

According to another embodiment of the invention a polymer compoundcomprising bio-based poly(ethylene terephthalate) of Formula VI isprovided.

wherein n is an integer of between about 50 and about 130.

In the bio-based poly(ethylene terephthalate) of Formula VI, at least 5%of the poly(ethylene terephthalate) is bio-based poly(ethyleneterephthalate). Preferably, at least 33% of the poly(ethyleneterephthalate) is bio-based poly(ethylene terephthalate). Morepreferably, at least 80% of the poly(ethylene terephthalate) isbio-based poly(ethylene terephthalate), and most preferably, at least90% of the poly(ethylene terephthalate) is bio-based poly(ethyleneterephthalate).

The ethylene group, —(CH₂)₂—, as shown in the Formula VI above may bepetroleum based, bio-based, or a combinations thereof, with bio-basedethylene, —(CH₂)₂—, being preferred.

According to another embodiment of the invention, a compound comprisingbio-based 1,4-cyclohexane dimethanol of Formula VII is also provided.

The bio-based 1,4-cyclohexane dimethanol of Formula VII above, isprepared from a biomass and at least 5% of the 1,4-cyclohexanedimethanol is bio-based 1,4-cyclohexane dimethanol. Preferably, at least80% of the 1,4-cyclohexane dimethanol is bio-based 1,4-cyclohexanedimethanol, and more preferably, at least 90% of the 1,4-cyclohexanedimethanol is bio-based 1,4-cyclohexane dimethanol,

According to another embodiment of the invention, a polymer compoundcomprising bio-based poly(cyclohexylene dimethyl terephthalate) ofFormula VIII is provided.

wherein n is an integer between about 50 and about 130; and

In the bio-based poly(cyclohexylene dimethyl terephthalate) shown inFormula VIII above, at least 5% of the poly(cyclohexylene dimethylterephthalate) is bio-based poly(cyclohexylene dimethyl terephthalate).Preferably, at least 80% of the poly(cyclohexylene dimethylterephthalate) is bio-based poly(cyclohexylene dimethyl terephthalate),and more preferably, at least 90% of the poly(cyclohexylene dimethylterephthalate) is Mo-based poly(cyclohexylene dimethyl terephthalate).

The bio-based poly(cyclohexylene dimethyl terephthalate) (bio-PCT) ofFormula VIII may be prepared by converting bio-based 1,4-cyclohexanedimethanol of Formula VII, or petroleum based 1,4-cyclohexanedimethanol, and/or a combination thereof with bio-based terephthalicacid (bio-TPA), or bio-based dimethyl terephthlate (bio-DMT) to producethe bio-PCT, preferably, bio-based 1,4-cyclohexane dimethanol isconverted with bio-TPA and/or bio-DMT to produce the bio-PCT.

According to the invention, the bio-based terephthalic acid (bio-TPA)and bio-based dimethyl terephthlate (bio-DMT) may be used to produceother bio-based polymers, such as bio-based PCTG, elastomericpolyesters, liquid crystalline polyarylates and their blends withtraditional thermoplastic polymers.

According to another embodiment of the invention, a process forpreparing bio-terephthalic acid (bio-TPA) and bio-dimethyl terephthalate(bio-DMT) is provided. An example of the process of the invention isrepresented in Scheme I below.

As shown in Scheme I, a biomass, containing a terpene, terpenoid, orcombination thereof, such as limonene, is converted in three steps tobio-terephthalic acid. The bio-terephthalic acid is then converted withmethanol to bio-dimethyl terephthalate. In this manner, bio-TPA andbio-DMT, two building blocks for bio-polymers are produced in highyield.

Step one of the process of the invention is shown in Scheme II below.

As shown in Scheme II, a terpene, such as α-limonene, obtained from abiological source, such as from lemons. The terpene may be selected fromthe group consisting of borneol, camphene, camphor, careen, camphene,carvacrol, carvone, cineole, eucalyptol, limonene, phellandrene,dipentene, pinene, sabinene, terpineol, terpinene, terpinolene, thujene,thymol, and combinations thereof. Preferably, the terpene or terpenoidhas a mono-cyclic or bi-cyclic structure, and/or the terpene orterpenoid has ten carbon atoms in the chemical formula. More preferably,the terpene is limonene.

The terpene, obtained from a biomass, is dehydrogenated with a catalyst,such as ethylenediamine and anhydrous FeCl₃ to produce bio-basedpara-cymene. Preferably, the dehydrogenation catalyst is a catalystselected from the group consisting of metal catalysts, amine catalysts,and combinations thereof. Preferably, the para-cymene is produced at ayield of at least 70% from the terpene, terpenoid, or combinationthereof, and more preferably, the para-cymene is produced at a yield ofat least 95% from the terpene, terpenoid, or combination thereof.

Steps two and three of the process of the invention are shown in SchemeIII below.

In step two of the process, para-cymene is converted to bio-TPA in thepresence of an oxidation catalyst, such as potassium permanganate. Thepara-cymene is converted to bio-based terephthalic acid substantially inthe absence of chromium oxide, and more preferably substantially in theabsence of chromium. Also preferably, The para-cymene is converted tobio-based terephthalic acid in a two-step oxidation comprising i) afirst step using a mineral acid, and ii) a second step using atransition metal oxidant. The two-step oxidation has been found to havea total yield of at least 85%.

The terephthalic acid produced by the above-described process is atleast 5% bio-based terephthalic acid, meaning that the bio-basedterephthalic acid is “isotopically rich” in carbon 14, by at least 5%,as compared to a petroleum source, as determined by ASTM D6866.Preferably, at least 90% of the terephthalic acid is bio-basedterephthalic acid, and more preferably, at least 95% of the terephthalicacid is bio-based terephthalic acid.

As also shown in Scheme II above, the bio-based terephthalic acid isconverted with methanol to bio-based dimethyl terephthalate selectedfrom the group consisting of bio-based methanol, petroleum basedmethanol, and combinations thereof to provide the bio-based dimethylterephthalate. Preferably, the bio-based terephthalic acid is convertedto bio-based dimethyl terephthalate of with methanol which is at least90% bio-based methanol.

In another embodiment of the invention, the bio-based terephthalic acidmay be mixed with petroleum based terephthalic acid to make a mixture ofbio-based terephthalic acid and petroleum based terephthalic acid. Inaddition, bio-based dimethyl terephthalate may be mixed with petroleumbased dimethyl terephthalate to make a mixture of bio-based dimethylterephthalate and petroleum based dimethyl terephthalate. These mixturesof bio-based and petroleum based terephthalic acid and dimethylterephthalate may be subsequently polymerized according to the inventionas described herein to make bio-based poly(alkylene terephthalates).

According to another embodiment of the invention, a process of making acompound comprising bio-based 1,4-cyclohexane dimethanol of Formula VIIis provided.

The process comprises providing a biomass comprising a terpene,terpenoid or a mixture thereof. Then, the terpene, terpenoid, or mixturethereof is converted to para-cymene and the para-cymene is converted tobio-terephthalic acid by oxidation, the oxidation being performed in theabsence of chromium oxide. The terephthalic acid is then dehydrogenatedto produce the bio-based 1,4-cyclohexane dimethanol of Formula VII.According to the invention, at least 5% of the 1,4-cyclohexanedimethanol is bio-based 1,4-cyclohexane dimethanol and the biomass is abiological material which excludes organic material that has beentransformed by geological processes into a member selected from thegroup consisting of petroleum, petrochemicals, and combinations thereof.

As shown in Scheme IV below, bio-based terephthalic acid and bio-baseddimethyl terephthalate may be converted by methods known to those ofskill in the art, such as a polycondensation reaction, ortransesterification, or other methods known to those of skill in the artto produce a variety of bio-based poly(alkylene terephthalate)s ofFormula III, also known as polyesters.

As shown in Scheme IV, the bio-based terephthalic acid and bio-baseddimethyl terephthalate are converted to bio-based poly(alkyleneterephthalate)s by reaction with a diol of the formula:

HO—R₁—OH

R₁, as shown in Scheme IV above, and also shown in the correspondingdiol structure above, is selected from the group consisting of alkyl,cycloalkyl, cycloalkylene alkyl, and cycloalkylene dialkyl groups havingfrom two to ten carbons, and n is an integer between about 50 and about130. Preferably, the alkyl group is an ethyl, propyl, or butyl group, ora cyclohexylene dimethyl group.

The diol may be petroleum based, bio-based, or a combination thereof.Preferably, the diol of the formula:

HO—R₁—OH

is at least 80% bio-based.

At least at least 5% of the poly(alkylene terephthalate) is bio-basedpoly(alkylene terephthalate). Preferably, at least 33% of thepoly(alkylene terephthalate) is bio-based poly(alkylene terephthalate).More preferably, at least 80% of the poly(alkylene terephthalate) isbio-based poly(alkylene terephthalate), and most preferably, at least90% of the poly(alkylene terephthalate) is bio-based poly(alkyleneterephthalate).

As shown in Table 1 below, the following poly(alkylene terephthalate)smay be produced according to the process of the invention shown above inScheme IV from either bio-TPA or bio-DMT, using the diol indicated inTable 1.

TABLE 1 Diol Formula Structure OH—R₁—OH Bio-based Content IV

HO—(CH₂)₄—OH At least 5% Preferably at least 60% More preferably atleast 80% Most preferably at least 90% V

HO—(CH₂)₃—OH At least 5% Preferably at least 60% More preferably atleast 80% Most preferably at least 90% VI

HO—(CH₂)₂—OH At least 5% Preferably at least 60% More preferably atleast 80% Most preferably at least 90% VIII

At least 5% Preferably at least 80% More preferably at least 90%

The diol shown in Table 1 above may be bio-based, petroleum based, or acombination thereof. Further, other diol not shown above are within thescope of the invention as will be understood by those of skill in theart by reference to this disclosure.

The invention will be further described by reference to the followingnon-limiting examples, which are offered to further illustrate variousembodiments of the present invention. It should be understood, however,that many variations and modifications can be made while remainingwithin the scope of the present invention,

EXAMPLES Example 1 Preparation of Bio-Based Terephthalic Acid fromLimonene

Example 1 shows that biologically-derived isotopically rich terephthalicacid was prepared from the terpene, limonene. The method involved twosteps, (i) the conversion of limonene to para-cymene and the (ii)conversion of para-cymene to terephthalic acid.

A. Conversion of Limonene to Para-Cymene.

Referring again to Scheme II, para-cymene, as shown below, was preparedfrom bio-based limonene as follows.

To mixture of ethylenediamine (525 mmol, 31.6 g, 35.2 ml), anhydrousFeCl₃ (0,964 mmol, 0.16 g) and sodium (145 mmol, 3.34 g) was heated toabout 50° C. under N₂. After sodium dissolution had started, asevidenced by hydrogen evolution and formation of a dark solution,α-limonene (742 mmol, 101 g, 120 ml), certified as derived from biomass(obtained from Sigma-Aldrich (St. Louis, Mo.), was added dropwise intothe mixture and the mixture heated to 100° C. The mixture was heated at100° C. for 8 h. The mixture was then cooled down and diluted with water(300 ml) and extracted two times with dichloro methane (DCM) (300 ml).The organic layers were dried over magnesium sulfate and concentratedusing a rotary evaporator obtaining the crude para-cymene product.Yield: 99% (purity 99%)

B. Conversion of Para-Cymene to Bio-Based Terephthalic Acid (Formula I).

Referring again to Scheme III, the para-cymene obtained in step A above,was converted to bio-based terephthalic acid of Formula I, shown below,as follows.

The oxidation stage was carried out in two steps as shown in Scheme III.To a solution of the crude of para-cymene product, obtained from thedehydrogenation of α-limonene, (742 mmol, 100 g) in water (400 ml) wasadded HNO₃ 65% (2968 mmol, 288 g, 206 ml). The reaction mixture washeated to reflux for 1 day and then the mixture was cooled down to roomtemperature and extracted twice with DCM (400 nil). Then, the organiclayers were washed two times with water (100 ml) and concentrated usinga rotary evaporator obtaining the crude product.

To the solution of crude product obtained from the oxidation ofpara-cymene in water (1000 ml) was added NaOH (1484 mmol, 83 g) and thesolution was stirred until the solid was dissolved. Potassiumpermanganate (1484 mmol, 235 g) was then added very slowly. The reactionmixture was heated to reflux for 16 h. The slurry mixture was thenfiltered on celite pad and washed with water. Concentrated H₂SO₄ (98%)was added to the aqueous layer until the pH of solution was stronglyacid and all solid was precipitated.

The white solid was filtered, washed with water and DCM (in order toremove the excess of acid and all not completed oxidized products). Theresulting pure white solid of bio-based terephthalic acid was dried at80° C., 50 mmHg for 12 h. Total yield (2 steps): 85%, 105 g.

Note:

The dehydrogenation step in step A, that produces para-cymene fromlimonene was also tested using Pd on charcoal (5% w/w) as a catalyst.The reaction was heated for 6 h at 100° C. under Nitrogen gas, but onlya low yield of para-cymene was obtained.

The direct oxidation of p-cymene to terephthalic acid was also attemptedusing a procedure reported in Ferguson, L. N., et al., Journal ofOrganic Chemistry (1960), 25, 668-70 and a low amount of product wasobtained. The best reaction condition were obtained using the two-stepprocedure described in step B above, comprising first addingconcentrated nitric acid to achieve the oxidation of isopropyl moietythen, next, treating this reaction mixture with potassium permanganateto produce the complete oxidation of the intermediate para-cymeneproducts.

C. Determination of the Biological Content of the Bio-Based TerephthalicAcid

ASTM-D6866 protocol was used to measure the “bio-based content” in amaterial, in an approach similar to the concept of radiocarbon datingwithout the use of the age equation. In this approach, the amount of ¹⁴Cin an unknown sample is expressed as a ratio to a modern referencestandard. The sample used as a modern reference standard in radiocarbondating is a standard from NIST (National Institute of Standards andTechnology) with a known radiocarbon content equivalent to the year AD1950. Material from AD 1950 was selected to be “zero years old” becauseit precedes the thermo-nuclear testing era when large excess ofradiocarbon was introduced to the atmosphere. Material from that year isalso represented by 100 pMC, Percent Modern Carbon. A fresh biomass suchas corn can give a signature of 107.5 pMC, which is higher level ofradiocarbon and is directly related to the thermo-nuclear weapon testingthat peaked in 1963. To express the results in biomass content, 100% isassigned to equal 107.5 pMC, while 0% is equal to 0 pMC. This result istermed “MEAN BIO-BASED RESULT.”

The results reported in this application as MEAN BIO-BASED RESULTinclude an absolute range of 6% to account for 3% on either side of theMEAN BIO-BASED RESULT to account for variations in end-productradiocarbon signature. All results are based on either bio-based contentin “present” material, not amount used in manufacturing process.

Procedure: Bio-based content was determined using ASTM-D6866 method.Samples were first combusted to CO₂, quantitatively recovering allcarbon species. The CO₂ was then reduced in a hydrogen atmosphere overmetal catalyst to produce graphite. The graphite was then analyzed in ahigh sensitivity Mass Spectrometer capable of separating the isotopescarbon-14 and carbon-12. Carbon-14 isotopes were measured as counts in asolid state detector and carbon-12 isotopes were measured as current ina Faraday cup (as microamps). ¹⁴C/¹²C ratios were derived for both amodern reference and the sample to derive the bio-based contentcalculated according to the following equation:

Bio-Based Content=(¹⁴C/¹²C ratio sample/¹⁴C/¹²C ratio modern)/1.075

Using the ASTM 16866 test protocols, the MEAN BIO-BASED CONTENT of thebio-based terephthalic acid was 93%.

Example 2 Comparative Example

The method of Example 1.0 was practiced, except that ordinarypetrochemical-derived terephthalic acid, obtained from Aldrich, was alsoevaluated for biological carbon content for comparison. Table 2 shows asummary of the results that were obtained from the measuring of thebiological content of Examples 1-2.

TABLE 2 MEAN BIO-BASED Composition Source CONTENT, % Limonene-derivedExample 1 93% terephthalic acid Petrochemical-derived Aldrich 0terephthalic acid

The results shown in Table 2 confirm that the bio-based terephthalicacid that was derived from limonene was isotopically rich, having a MEANBIO-BASED CONTENT of at least 93% while the terephthalic acid derivedfrom petrochemical sources did not have any.

Examples 1 and 2 above confirm that the process described herein is aneffective way for making biologically derived terephthalic acid fromlimonene.

Example 3 Bio-Based Dimethyl Terephthalate (Formula II)

Referring again to Scheme IV, a synthesis of bio-based dimethylTerephthalate (Formula II, as shown below) was prepared from bio-basedterephthalic acid (Formula I) as follows.

To a solution of the bio-based terephthalic acid (632 mmol, 105 g)(obtained in Example 1) in methanol (6320 mmol, 2086 ml) was addedconcentrated H₂SO₄ (31.6 mmol, 3.23 ml) and the mixture was stirred for1 day at reflux. After cooling down the solution, the solvent wasremoved and the resulting solid was dissolved in dichloro methane (DCM)(400 ml). The solution was washed with water (200 ml or until pH ofsolution is neutral), then the organic layer was dried over magnesiumsulfate and concentrated using a rotary evaporator to obtain the crudeproduct, a solid. The solid was purified washing it with a small amountof cold methanol and dried at 90° C., for 12 h. The yield that wasobtained was 95% (117 g).

Example 4 Comparative Example

The method of Example 3 was practiced, except that ordinarypetrochemical-derived dimethyl terephthalate, obtained from Aldrich, wasalso evaluated for biological carbon content using ASTM 6866 forcomparison. Table 2 shows a summary of the results that were obtained.

TABLE 3 MEAN BIO-BASED Composition Source CONTENT, % Limonene-derivedExample 3 81% dimethyl terephthalate Petrochemical-derived Aldrich 0dimethyl terephthalate

The results confirm that the isotopically rich dimethyl terephthalatethat was derived from limonene had a MEAN BIO-BASED CONTENT of at least81% while the dimethyl terephthalate from petrochemical sources did nothave any. Examples 3 and 4 show that the process described herein is aneffective way for making bio-based dimethyl terephthalate (bio-DMT) fromlimonene,

Example 5 Bio-Based Poly(Butylene Terephthalate) (Bio-PBT)

Bio-based poly(butylene terephthalate) (bio-PBT) (Formula IV, as shownbelow) was prepared from bio-based dimethyl terephthalate (Formula II)as follows.

Bio-PBT was made starting from bio-DMT, obtained from limonene (100mmol, 19.4 g) and 1,4-butanediol (BDO) (160 mmol, 14.4 g) (DMT/BDO=1.6molar ratio), triisopropyl titanate (TPT), made by Dupont as atranesterification catalyst (0.027 g, 175 ppm of titanium) was added.The synthesis was carried out with a two-stage polycondensationprocedure in a 250 ml round-bottom wide-neck reactor, closed at the topwith three-neck flat flange lid equipped with a mechanical stirrer(100-50 rpm).

The lid was heated at a temperature of 90° C. in the first stage and120° C. in the second stage, with a heating band. A condenser (liquidnitrogen cooled) was connected to the reactor to collect volatileproducts during the first and the second stage. The reactor was heatedby thermostated oil bath in which the system was placed.

In the first stage, conducted at atmospheric pressure, the temperatureof oil bath was kept at 180° C., after 10 min at 210° C. for 90 min. Inthe second stage, the pressure was slowly reduced from atmospheric toless than 1 mbar and the temperature was raised to 245° C. for 60 min.The viscous polymer was pulled out of the reaction mixture.

According to another embodiment of the invention, bio-PBT was made usingthe above described procedure, but the raw materials were petroleumderived DMT and bio-based BDO. Bio-based BDO can be made frombiologically sourced C4 acids such as succinic acid or maleic acid orfumaric acid, etc by hydrogenation.

According to another embodiment of the invention, bio-PBT was made usingthe above described polymerization procedure, but the raw materials wereboth bio-based DMT and bio-based BDO in order to increase the greencontent of PBT to maximum.

Example 6 Comparative Example

The method of Example 5 was practiced, except that ordinarypetrochemical-derived PBT, obtained from Sabic Innovative Plastics, USA,was also evaluated for biological carbon content using ASTM 6866 forcomparison. Table 4 shows a summary of the results that were obtained.

TABLE 4 MEAN BIO-BASED Composition Source CONTENT, % PBT made fromExample 5 66 Limonene-derived DMT + Petrochemical derived BDOPetrochemical-derived Sabic, USA 0 PBT PBT made from Example 5 28Petrochemical derived DMT + Bio derived BDO PBT made from Example 5 94Limonene-derived DMT + Bio derived BDO

The results confirm that the bio-PBT had a MEAN BIO-BASED CONTENT of atleast 28% while the PBT from petrochemical sources (Sabic, USA) did nothave any. The experiment confirms that the process described above is aneffective way for making bio-based PBT,

Example 7 Bio-Based Polyethylene Terephthalate) (Bio-PET)

Bio-based poly(ethylene terephthalate) (bio-PET, Formula V, shown below)was prepared from bio-based dimethyl terephthalate (Formula II) asfollows.

Bio-PET was made starting from bio-DMT, obtained from limonene (120mmol, 23.3 g) and 1,2-ethylene glycol (EG) (264 mmol, 16.4 g)(DMT/EG=2.2 molar ratio), with TPT (0.019 g, 100 ppm of titanium). Thesynthesis was carried out with a two-stage polycondensation procedure ina 250 ml round-bottom wide-neck reactor, closed at the top withthree-neck flat flange lid equipped with a mechanical stirrer (100-50rpm). The lid was heated at a temperature of 90° C. in the first stageand 120° C. in the second stage, with a heating band. A condenser(liquid nitrogen cooled) was connected to the reactor to collectvolatile products during the first and the second stage. The reactor washeated by thermostated oil bath in which the system was placed.

In the first stage, conducted at atmospheric pressure, the temperatureof oil bath was kept at 165° C., after 5 min at 210° C. for 160 min. Inthe second stage, the pressure was slowly reduced from atmospheric toless than 1 mbar and the temperature was raised to 280° C. for 90 minThe viscous polymer was pulled out of the reaction flask.

Example 8 Comparative Example

The method of Example 7 was practiced, except that ordinarypetrochemical-derived PET, obtained from Futura Polyesters, Chennai,India, was also evaluated for biological carbon content using ASTM 6866for comparison. Table 5 shows a summary of the results that wereobtained.

TABLE 5 MEAN BIO-BASED Composition Source CONTENT, % PET made fromExample 3 79 Limonene-derived DMT + Petrochemical derived EGPetrochemical-derived Futura Polyesters, 0 PET India

The results confirm that the bio-PET that was derived from limonene hada MEAN BIO-BASED CONTENT of at least 79%, while the PET frompetrochemical sources (Futura Polyesters, India) did not have any. Theexperiment confirms that the process described above is an effective wayfor making bio-based PET.

Example 9 Bio-Based Poly(Trimethylene Terephthalate) (Bio-PTT)

Bio-based poly(trimethylene terephthalate) (bio-PTT, Formula VI, shownbelow) was prepared from bio-DMT as follows.

Bio-PTT was made starting from DMT obtained from limonene (100 mmol,19.4 g) and 1,3-propylene glycol (PDO) (170 mmol, 13.2 g) (DMT/PD=1.7molar ratio), with TPT (0.015 g, 94 ppm of titanium).

The synthesis was carried out with a two-stage polycondensationprocedure in a 250 ml round-bottom wide-neck reactor, closed at the topwith three-neck flat flange lid equipped with a mechanical stirrer(100-50 rpm).

The lid was heated at a temperature of 90° C. in the first stage and120° C. in the second stage, with a heating band. A condenser (liquidnitrogen cooled) was connected to the reactor to collect volatileproducts during the first and the second stage. The reactor was heatedby thermostated oil bath in which the system was placed.

In the first stage, conducted at atmospheric pressure, the temperatureof oil bath was kept at 180° C., after 10 min at 205° C. for 90 min. Inthe second stage, the pressure was slowly reduced from atmospheric toless than 1 mbar and the temperature was raised to 245° C. for 90 min.The viscous polymer was pulled out of the flask.

Example 10 Comparative Example

The method of Example 9 was practiced, except that ordinarypetrochemical-derived PIT, obtained from Futura Polyesters, Chennai,India, was also evaluated for biological carbon content using ASTM 6866for comparison. Table 6 shows a summary of the results that wereobtained.

TABLE 6 MEAN BIO-BASED Composition Source CONTENT, % PTT made fromExample 3 71 Limonene-derived DMT + Petrochemical derived PDOPetrochemical-derived Futura Polyesters 0 PTT

The results confirm that the Bio-PTT that was derived from limonene hada MEAN BIO-BASED CONTENT of at least 71% while the PTT frompetrochemical sources (Futura Polyesters, India) did not have any. Theexperiment confirms that the process described above is an effective wayfor making bio-based PTT.

Example 11 Bio-Based Poly(Cyclohexylene Dimethyl Terephthalate)(Bio-PCT)

Bio-based poly(cyclohexylene dimethyl terephthalate) (bio-PCT, FormulaVIII, shown below) was made from bio-DMT as follows.

Bio-PCT was synthesized starting from bio-DMT obtained from limonene(100 mmol, 19.4 g) and 1,6-cyclohexane dimethanol (CHDM) (170 mmol, 13.2g) (DMT/CHDM=1.7 molar ratio), with TPT (0.015 g, 94 ppm of titanium).

The synthesis was carried out with a two-stage polycondensationprocedure in a 250 ml round-bottom wide-neck reactor, closed at the topwith three-neck flat flange lid equipped with a mechanical stirrer(100-50 rpm).

The lid was heated at a temperature of 90° C. in the first stage and120° C. in the second stage, with a heating band. A condenser (liquidnitrogen cooled) was connected to the reactor to collect volatileproducts during the first and the second stage. The reactor was heatedby thermostated oil bath in which the system was placed.

In the first stage, conducted at atmospheric pressure, the temperatureof oil bath was kept at 180° C., after 10 min at 205° C. for 90 min. Inthe second stage, the pressure was slowly reduced from atmospheric toless than 1 mbar and the temperature was raised to 300° C. for 30 min,The viscous polymer was pulled out of the flask.

Example 12 Comparative Example

The method of Example 11 was practiced, except that ordinarypetrochemical-derived PCT, obtained from Eastman, USA, was alsoevaluated for biological carbon content using ASTM 6866 for comparison.Table 7 shows a summary of the results that were obtained.

TABLE 7 MEAN BIO-BASED Composition Source CONTENT, % PCT made fromExample 3 49 Limonene-derived DMT + Petrochemical derived CHDMPetrochemical-derived Eastman 0 PCT

The results confirm that the bio-PCT that was derived from limonene hada MEAN BIO-BASED CONTENT of at least 49% while the PCT frompetrochemical sources (Eastman, USA) did not have any. The experimentconfirms that the process described above is an effective way for makingbio-based PCT.

Example 13 Bio-Based Polymer Characterization

The poly(alkylene terephthalates) prepared and/or analyzed in the aboveExamples 5-9 were analyzed and characterized according to known methods,or the information below was obtained from the manufacturerspecifications. The comparative results are shown in Table 8 below.

TABLE 8 General characterization of Polyesters. TGA DSC GPC T_(peak)T_(onset) T_(g) T_(m) T_(c) M_(w) M_(n) PDI (° C.) (° C.) (° C.) (° C.)(° C.) bio-PBT 113000 46700 2.4 415 395 — 222 181 (Example 5) PBT 19557000 28000 2.1 413 392 — 223 174 (Example 6) bio-PET 93000 38000 2.4452 423 82 251 174 (Example 7) PET 62000 30000 2.0 451 426 84 257 192(Example 8) PTT 70000 32000 2.2 413 390 — 230 158 (Example 9)

The data in Table 8 shows that the poly(terephthalates) preparedaccording to the invention have similar properties and thus similarlyapplicable applications, such as in fabrics, blow molded plastics, andother uses.

Although the present invention has been discussed in considerable detailwith reference to certain preferred embodiments, other embodiments arepossible. Therefore, the scope of the appended claims should not belimited to the description of preferred embodiments contained herein.

1-19. (canceled)
 20. A process of making a polymer from a bio-basedterephthalic acid composition, the process comprising: (a) providing abiomass comprising limonene; (b) converting the limonene to para-cymeneat a yield of at least 95%; and (c) converting the para-cymene toterephthalic acid at a total yield of at least 85% by oxidation in atwo-step oxidation comprising: (i) a first step using a mineral acid,and (ii) a second step using a transition metal oxidant; the oxidationbeing performed substantially in the absence of chromium oxide; (d)converting the bio-based terephthalic acid with methanol selected fromthe group consisting of bio-based methanol, petroleum based methanol,and combinations thereof to provide bio-based dimethyl terephthalate;wherein the bio-based terephthalic acid has a mean bio-based content ofat least 95%; and wherein the biomass is a biological material whichexcludes organic material that has been transformed by geologicalprocesses into a member selected from the group consisting of petroleum,petrochemicals, and combinations thereof; and (e) converting thebio-based dimethyl terephthalate of Formula II to a bio-basedpoly(alkylene terephthalate) of Formula III

by reacting the bio-based dimethyl terephthalate with a diol of theformula:HO—R₁—OH wherein R₁ is selected from the group consisting of alkyl,cycloalkyl, cycloalkylene alkyl, and cycloalkylene dialkyl groups havingfrom two to ten carbons, n is an integer between about 50 and about 130;and wherein the bio-based poly(alkylene terephthalate) has a meanbio-based content of at least 5%.
 21. A process according to claim 20wherein the bio-based poly(alkylene terephthalate) has a mean bio-basedcontent of at least 33%.
 22. A process according to claim 20 wherein thebio-based poly(alkylene terephthalate) has a mean bio-based content ofat least 80%.
 23. A process according to claim 20 wherein the bio-basedpoly(alkylene terephthalate) has a mean bio-based content of at least90%.
 24. A process according to claim 20 wherein the diol of theformula:HO—R₁—OH is at least in part a bio-based diol, the diol having a meanbio-based content of at least 80%.
 25. A process of making a polymerfrom a bio-based terephthalic acid composition, the process comprising:(a) providing a biomass comprising limonene; (b) converting the limoneneto para-cymene at a yield of at least 95%; and (c) converting thepara-cymene to terephthalic acid at a total yield of at least 85% byoxidation in a two-step oxidation comprising: (i) a first step using amineral acid, and (ii) a second step using a transition metal oxidant;the oxidation being performed substantially in the absence of chromiumoxide; (d) converting the bio-based terephthalic acid with methanolselected from the group consisting of bio-based methanol, petroleumbased methanol, and combinations thereof to provide bio-based dimethylterephthalate; wherein the bio-based terephthalic acid has a meanbio-based content of at least 95%; and wherein the biomass is abiological material which excludes organic material that has beentransformed by geological processes into a member selected from thegroup consisting of petroleum, petrochemicals, and combinations thereof;and (e) converting the bio-based dimethyl terephthalate to bio-basedpoly(butylene terephthalate) of Formula IV:

by reacting the bio-based dimethyl terephthalate with 1,4-butane diol,wherein n is an integer between about 50 and about 130; and wherein thebio-based poly(butylene terephthalate) has a mean bio-based content ofat least 5%.
 26. A process according to claim 25 wherein the bio-basedpoly(butylene terephthalate) has a mean bio-based content of at least60%.
 27. A process according to claim 25 wherein the bio-basedpoly(butylene terephthalate) has a mean bio-based content of at least80%.
 28. A process according to claim 25 wherein the bio-basedpoly(butylene terephthalate) has a mean bio-based content of at least90%.
 29. A process according to claim 25 wherein the 1,4-butane diol isselected from the group consisting of petroleum based 1,4-butane diol,bio-based 1,4-butane diol, and combinations thereof.
 30. A processaccording to claim 25 wherein the 1,4-butane diol is at least in partbio-based 1,4-butane diol.
 31. A process of making a polymer from abio-based terephthalic acid composition, the process comprising: (a)providing a biomass comprising limonene; (b) converting the limonene topara-cymene at a yield of at least 95%; and (c) converting thepara-cymene to terephthalic acid at a total yield of at least 85% byoxidation in a two-step oxidation comprising: (i) a first step using amineral acid, and (ii) a second step using a transition metal oxidant;the oxidation being performed substantially in the absence of chromiumoxide; (d) converting the bio-based terephthalic acid with methanolselected from the group consisting of bio-based methanol, petroleumbased methanol, and combinations thereof to provide bio-based dimethylterephthalate; wherein the bio-based terephthalic acid has a meanbio-based content of at least 95%; and wherein the biomass is abiological material which excludes organic material that has beentransformed by geological processes into a member selected from thegroup consisting of petroleum, petrochemicals, and combinations thereof;and (e) converting the bio-based dimethyl terephthalate to bio-basedpoly(trimethylene terephthalate) of Formula V:

by reacting the bio-based dimethyl terephthalate with 1,3-propane diol,wherein n is an integer between about 50 and 130, and wherein thebio-based poly(trimethylene terephthalate) has a mean bio-based contentof at least 5%.
 32. A process according to claim 31 wherein thebio-based poly(trimethylene terephthalate) has a mean bio-based contentof at least 50%.
 33. A process according to claim 31 wherein thebio-based poly(trimethylene terephthalate) has a mean bio-based contentof at least 80%.
 34. A process according to claim 31 wherein thebio-based poly(trimethylene terephthalate) has a mean bio-based contentof at least 90%.
 35. A process according to claim 31 wherein the1,3-propane diol is selected from the group consisting of petroleumbased 1,3-propane diol, bio-based 1,3-propane diol, and combinationsthereof.
 36. A process according to claim 31 wherein the 1,3-propanediol is at least in part bio-based 1,3-propane diol.
 37. A processaccording to claim 31 wherein the 1,3-propane diol is at least in partbio-based 1,3-propane diol, the 1,3-propane diol having a mean bio-basedcontent of at least 80%.
 38. A process of making a polymer from abio-based terephthalic acid composition, the process comprising: (a)providing a biomass comprising limonene; (b) converting the limonene topara-cymene at a yield of at least 95%; and (c) converting thepara-cymene to terephthalic acid at a total yield of at least 85% byoxidation in a two-step oxidation comprising: (i) a first step using amineral acid, and (ii) a second step using a transition metal oxidant;the oxidation being performed substantially in the absence of chromiumoxide; (d) converting the bio-based terephthalic acid with methanolselected from the group consisting of bio-based methanol, petroleumbased methanol, and combinations thereof to provide bio-based dimethylterephthalate; wherein the bio-based terephthalic acid has a meanbio-based content of at least 95%; and wherein the biomass is abiological material which excludes organic material that has beentransformed by geological processes into a member selected from thegroup consisting of petroleum, petrochemicals, and combinations thereof;and (e) converting the bio-based dimethyl terephthalate to bio-basedpoly(ethylene terephthalate) of Formula VI:

by reacting the bio-based dimethyl terephthalate with ethylene glycol,wherein n is an integer between about 50 and 130; and wherein thebio-based poly(ethylene terephthalate) has a mean bio-based content ofat least 5%.
 39. A process according to claim 38 wherein the bio-basedpoly(ethylene terephthalate) has a mean bio-based content of at least70%.
 40. A process according to claim 38 wherein the bio-basedpoly(ethylene terephthalate) has a mean bio-based content of at least80%.
 41. A process according to claim 38 wherein the bio-basedpoly(ethylene terephthalate) has a mean bio-based content of at least90%.
 42. A process according to claim 38 wherein the ethylene glycol isselected from the group consisting of petroleum based ethylene glycol,bio-based ethylene glycol, and combinations thereof.
 43. A processaccording to claim 38 wherein the ethylene glycol is at least in partbio-based ethylene glycol.
 44. A process according to claim 38 whereinthe ethylene glycol is at least in part bio-based ethylene glycol, theethylene glycol having a mean bio-based content of at least 80%.
 45. Aof making a polymer from a bio-based terephthalic acid composition, theprocess comprising: (a) providing a biomass comprising limonene; (b)converting the limonene to para-cymene at a yield of at least 95%; and(c) converting the para-cymene to terephthalic acid at a total yield ofat least 85% by oxidation in a two-step oxidation comprising: (i) afirst step using a mineral acid, and (ii) a second step using atransition metal oxidant; the oxidation being performed substantially inthe absence of chromium oxide; (d) converting the bio-based terephthalicacid with methanol selected from the group consisting of bio-basedmethanol, petroleum based methanol, and combinations thereof to providebio-based dimethyl terephthalate; wherein the bio-based terephthalicacid has a mean bio-based content of at least 95%; and wherein thebiomass is a biological material which excludes organic material thathas been transformed by geological processes into a member selected fromthe group consisting of petroleum, petrochemicals, and combinationsthereof; and (e) converting the bio-based dimethyl terephthalate tobio-based poly(cyclohexylene dimethylene terephthalate) of Formula VIII:

by reacting the bio-based dimethyl terephthalate with 1,4-cyclohexanedimethanol, wherein n is an integer between about 50 and 130, andwherein the bio-based poly(1,4-cyclohexylene dimethylene terephthalate)has a mean bio-based content of at least 5%.
 46. A process according toclaim 45 wherein the bio-based poly(1,4-cyclohexylene dimethyleneterephthalate) has a mean bio-based content of at least 50%.
 47. Aprocess according to claim 45 wherein the bio-basedpoly(1,4-cyclohexylene dimethylene terephthalate) has a mean bio-basedcontent of at least 80%.
 48. A process according to claim 45 wherein thebio-based poly(1,4-cyclohexylene dimethylene terephthalate) has a meanbio-based content of at least 90%.
 49. A process according to claim 45wherein the 1,4-cyclohexane dimethanol is selected from the groupconsisting of petroleum based 1,4-cyclohexane dimethanol, bio-based1,4-cyclohexane dimethanol, and combinations thereof.
 50. A processaccording to claim 45 wherein the 1,4-cyclohexane dimethanol is at leastin part bio-based 1,4-cyclohexane dimethanol.
 51. A process according toclaim 45 wherein the 1,4-cyclohexane dimethanol is at least in partbio-based 1,4-cyclohexane dimethanol, the 1,4-cyclohexane having a meanbio-based content of at least 80%.
 52. A process of making a polymerfrom a bio-based terephthalic acid composition, the process comprising:(a) providing a biomass comprising limonene; (b) converting the limoneneto para-cymene at a yield of at least 95%; and (c) converting thepara-cymene to terephthalic acid at a total yield of at least 85% byoxidation in a two-step oxidation comprising: (i) a first step using amineral acid, and (ii) a second step using a transition metal oxidant;the oxidation being performed substantially in the absence of chromiumoxide; (d) converting the bio-based terephthalic acid with methanolselected from the group consisting of bio-based methanol, petroleumbased methanol, and combinations thereof to provide bio-based dimethylterephthalate; wherein the bio-based terephthalic acid has a meanbio-based content of at least 95%; and wherein the biomass is abiological material which excludes organic material that has beentransformed by geological processes into a member selected from thegroup consisting of petroleum, petrochemicals, and combinations thereof;and (d) converting the bio-based terephthalic acid to a poly(alkyleneterephthalate) of Formula III:

by reacting the bio-based terephthalic acid with a diol of the formula:HO—R₁—OH wherein R₁ is selected from the group consisting of alkyl,cycloalkyl, cycloalkylene alkyl, and cycloalkylene dialkyl groups havingfrom two to ten carbons, n is an integer between about 50 and about 130;and wherein the bio-based poly(alkylene terephthalate) has a meanbio-based content of at least 40%.
 53. A process according to claim 52wherein the bio-based poly(alkylene terephthalate) has a mean bio-basedcontent of at least 33%.
 54. A process according to claim 52 wherein thebio-based poly(alkylene terephthalate) has a mean bio-based content ofat least 80%.
 55. A process according to claim 52 wherein the bio-basedpoly(alkylene terephthalate) has a mean bio-based content of at least90%.
 56. A process according to claim 52 wherein the diol of theformula:HO—R₁—OH is at least partially bio-based, the diol having a meanbio-based content of at least 80%.
 57. The process of claim 56 whereinthe diol comprises a component of both bio-based diols andpetrochemically-derived diols.